(μ-η²-4,4-dimethylpent-1-yne)dicobalt hexacarbonyl | 152015-28-6

• 英文名称: (μ-η²-4,4-dimethylpent-1-yne)dicobalt hexacarbonyl
• CAS: 152015-28-6
• 化学式: C₁₃H₁₂Co₂O₆
• 分子量: 382.221
• InChiKey: DJHHWVVXDNWIRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (μ-η²-4,4-dimethylpent-1-yne)dicobalt hexacarbonyl 、 一氧化碳 以 正己烷 为溶剂， 以87%的产率得到
  参考文献：
  名称：

  On the reactivity of acetylenes coordinated to cobalt.

  摘要：

  Acetylenes (R1C2R2, R1 = H, R2 = n-Pr, i-Pr, t-Bu, neo-Pent) with equimolar Co2(CO)8 or the corresponding (R1C2R2)Co2(CO)6 (1) complexes were found to undergo stoichiometric cyclocarbonylation (n-hexane, 100-degrees-C, p(CO) 27 MPa) to give almost quantitative yields of [mu2-(2-R2-2-butene-4-olide-4-ylidene)] [mu2-carbonyl] dicobalt hexacarbonyl (Co-Co) (2) complexes with nearly quantitative yields and 100% regioselectivity. The absence of the influence of the steric bulk of substituent R2 on the carbonylation is commented in terms of mechanistic speculations.

  DOI：

  10.1016/0304-5102(93)80077-8
• 作为产物：
  描述：

  4,4-dimethylpent-1-yn-3-ol 在 双(环戊二烯)钴 作用下， 以 乙醚 、 二氯甲烷 、 正戊烷 为溶剂， 反应 12.42h， 生成 (μ-η²-4,4-dimethylpent-1-yne)dicobalt hexacarbonyl 、 (μ-η²-3-methoxy-4,4-dimethylpent-1-yne)dicobalt hexacarbonyl
  参考文献：
  名称：

  获取和利用丙炔基自由基的持久性：新型范式

  摘要：

  Three complementary methods for altering an intrinsic nature of propargyl radicals, from transient to persistent, were developed by fine-tuning the bulkiness and degree of substitution around the secondary and tertiary propargylic carbons, as well as by sterically enhancing a pi-bonded Co-2(CO)(6) metal core. The latter was employed, as a mechanistic tool, for precluding an acetylene allene rearrangement, stabilizing propargyl cations, and creating a steric hindrance that could provide for said transition from transient to persistent propargyl radicals. A window of opportunities was identified wherein the steric bulkiness in propargyl radicals remains below the "persistency threshold", providing good to excellent stereoselectivities in radical dimerization reactions (d,l 62-100%). Along with the persistency threshold for tertiary propargyl radicals (278.2 angstrom(3)), two different thresholds for persistency in secondary propargyl radicals were established-306.5 and 576.0 angstrom(3)-dependent upon the molecular architecture and the nature of the substituents populating the radical centers. Three alternative molecular platforms were designed to exploit a newly acquired dichotomy in allylic radicals (alpha-persistent-gamma-transient) and trichotomy in pentadienyl radicals (alpha-persistent-gamma-transient-epsilon- transient), providing access to molecular assemblies with contiguous 4 degrees-4 degrees, 4 degrees-3 degrees, and 3 degrees-3 degrees carbon atoms.

  DOI：

  10.1021/acs.organomet.6b00435